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A robust assessment is made of the distribution and (spatially resolved) geologic context for the newly identified rock type on the Moon, a Mg-spinel-bearing anorthosite (pink-spinel anorthosite, PSA). Essential criteria for confirmed detection of Mg-spinel using spectroscopic techniques are presented and these criteria are applied to recent data from the Moon Mineralogy Mapper. Altogether, 23 regions containing confirmed exposures of the new Mg-spinel rock type are identified. All exposures are in highly feldspathic terrain and are small—a few hundred meters—but distinct and verifiable, most resulting from multiple measurements. Each confirmed detection is classified according to geologic context along with other lithologies identified in the same locale. Confirmed locations include areas along the inner rings of four mascon basins, knobs within central peaks of a few craters, and dispersed exposures within the terraced walls of several large craters. Unexpected detections of Mg-spinel are also found at a few areas of hypothesized non-mare volcanism. The small Mg-spinel exposures are shown to be global in distribution, but generally associated with areas of thin crust. Confirmation of Mg-spinel exposures as part of the inner ring of four mascon basins indicates this PSA rock type is principally of lower crust origin and predates the basin-forming era.

The decay of short-lived iodine (I) and plutonium (Pu) results in xenon (Xe) isotopic anomalies in the mantle that record Earth's earliest stages of formation. Xe isotopic anomalies have been linked to degassing during accretion, but degassing alone cannot account for the co-occurrence of Xe and tungsten (W) isotopic heterogeneity in plume-derived basalts and their long-term preservation in the mantle. Here we describe measurements of I partitioning between liquid Fe alloys and liquid silicates at high pressure and temperature and propose that Xe isotopic anomalies found in modern plume rocks (that is, rocks with elevated 3He/4He ratios) result from I/Pu fractionations during early, high-pressure episodes of core formation. Our measurements demonstrate that I becomes progressively more siderophile as pressure increases, so that portions of mantle that experienced high-pressure core formation will have large I/Pu depletions not related to volatility. These portions of mantle could be the source of Xe and W anomalies observed in modern plume-derived basalts. Portions of mantle involved in early high-pressure core formation would also be rich in FeO, and hence denser than ambient mantle. This would aid the long-term preservation of these mantle portions, and potentially points to their modern manifestation within seismically slow, deep mantle reservoirs with high 3He/4He ratios.

The distribution of rare earth elements (REEs) between amphibole and silicate melt is important for understanding a wide variety of igneous and metamorphic processes in the lithosphere. In this study, we used published experimental REE and Y partitioning data between amphibole and silicate melt, the lattice strain model, and nonlinear least-squares regression method to parameterize key partitioning parameters in the lattice strain model ( D 0 , r 0 , and E ) as a function of pressure, temperature, and both amphibole and melt compositions. Two models, which give nearly identical results, are obtained in this study. In the first model, D 0 depends on temperature and amphibole composition: it positively correlates with Ti content and negative correlates with temperature and Mg, Na, and K contents in the amphibole. In the second model, D 0 depends solely on the melt composition: it positively correlates with Si content and negatively correlates with Ti and Ca contents in the melt. In both the mineral and melt composition models, r 0 negatively correlates with the ferromagnesian content in the M4 site of the amphibole, and E is a constant. The very similar coefficients in the equations for r 0 and best-fit values for E in the two models allow us to connect the two models through amphibole-melt phase equilibria. An application of our model to amphiboles in mantle xenoliths shows that observed major element compositional variations in amphibole alone can give rise to order of magnitude variations in amphibole-melt REE partition coefficients. Together with experimental data simulating fractional crystallization of arc magmas, out models suggest that: (1) REE partition coefficients between amphibole and melt can vary by an order of magnitude during arc magma crystallization due to variation in the temperature and composition of the amphibole and melt, and that (2) amphibole fractional crystallization plays a key role in depleting the middle REEs relative to heavy REEs and light REEs in arc magmas.

Subduction of hydrous and carbonated oceanic lithosphere replenishes the mantle volatile inventory. Substantial uncertainties exist on the magnitudes of the recycled volatile fluxes and it is unclear whether Earth surface reservoirs are undergoing net-loss or net-gain of H2O and CO2. Here, we use noble gases as tracers for deep volatile cycling. Specifically, we construct and apply a kinetic model to estimate the effect of subduction zone metamorphism on the elemental composition of noble gases in amphibole – a common constituent of altered oceanic crust. We show that progressive dehydration of the slab leads to the extraction of noble gases, linking noble gas recycling to H2O. Noble gases are strongly fractionated within hot subduction zones, whereas minimal fractionation occurs along colder subduction geotherms. In the context of our modelling, this implies that the mantle heavy noble gas inventory is dominated by the injection of noble gases through cold subduction zones. For cold subduction zones, we estimate a present-day bulk recycling efficiency, past the depth of amphibole breakdown, of 5–35% and 60–80% for 36Ar and H2O bound within oceanic crust, respectively. Given that hotter subduction dominates over geologic history, this result highlights the importance of cooler subduction zones in regassing the mantle and in affecting the modern volatile budget of Earth's interior.

We report results from multi-anvil (MA) and laser-heated diamond anvil cell (LH-DAC) experiments that synthesize high-pressure phases, including bridgmanite, ferropericlase, stishovite, and ultramafic liquid, in the presence of an argon-rich fluid. The goal of the experiments is to constrain the equilibrium distribution of argon in magma ocean environments. Argon concentrations in LH-DAC experiments were quantified by electron microprobe analysis, while argon concentrations in MA experiments were quantified by laser-ablation mass spectrometry and electron microprobe analysis. Our LH-DAC experiments demonstrate that argon solubility in ultramafic liquid is near or above 1.5 wt.% at conditions between 13–101 GPa and 2300–6300 K. Argon concentrations in bridgmanite and ferropericlase synthesized in LH-DAC experiments range from below detection to 0.58 wt.%. Argon concentrations in bridgmanite and ferropericlase synthesized in MA experiments range from below detection to 2.16 wt.% for electron microprobe measurements and laser-ablation measurements. We interpret this wide range of argon concentrations in minerals to reflect the variable presence of argon-rich fluid inclusions in analytical volumes. Our analyses therefore provide upper limit constraints for argon solubility in high-pressure minerals ( D bridgmanite − melt Ar D ferropericlase − melt Ar

Measurements of Xe isotope ratios in ocean island basalts (OIB) suggest that Earth’s mantle accreted heterogeneously, and that compositional remnants of accretion are sampled by modern, high-3He/4He OIB associated with the Icelandic and Samoan plumes. If so, the high-3He/4He source may also have a distinct oxygen isotopic composition from the rest of the mantle. Here, we test if the major elements of the high-3He/4He source preserve any evidence of heterogeneous accretion using measurements of three oxygen isotopes on olivine from a variety of high-3He/4He OIB locations. To high precision, the Δ17O value of high-3He/4He olivines from Hawaii, Pitcairn, Baffin Island and Samoa, are indistinguishable from bulk mantle olivine (Δ17OBulk Mantle − Δ17OHigh 3He/4He olivine = −0.002 ± 0.004 (2 × SEM)‰). Thus, there is no resolvable oxygen isotope evidence for heterogeneous accretion in the high-3He/4He source. Modelling of mixing processes indicates that if an early-forming, oxygen-isotope distinct mantle did exist, either the anomaly was extremely small, or the anomaly was homogenised away by later mantle convection.\ud \ud The δ18O values of olivine with the highest 3He/4He ratios from a variety of OIB locations have a relatively uniform composition (∼5‰). This composition is intermediate to values associated with the depleted MORB mantle and the average mantle. Similarly, δ18O values of olivine from high-3He/4He OIB correlate with radiogenic isotope ratios of He, Sr, and Nd. Combined, this suggests that magmatic oxygen is sourced from the same mantle as other, more incompatible elements and that the intermediate δ18O value is a feature of the high-3He/4He mantle source. The processes responsible for the δ18O signature of high-3He/4He mantle are not certain, but δ18O–87Sr/86Sr correlations indicate that it may be connected to a predominance of a HIMU-like (high U/Pb) component or other moderate δ18O components recycled into the high-3He/4He source.

Visible to near-infrared (V-NIR) remote sensing observations have identified spinel in various locations and lithologies on the Moon. Experimental studies have quantified the FeO content of these spinels (Jackson et al. 2014), however the chromite component is not well constrained. Here we present compositional and spectral analyses of spinel synthesized with varying chromium contents at lunar-like oxygen fugacity ( f O2). Reflectance spectra of the chromium-bearing synthetic spinels (Cr# 1–29) have a narrow (~130 nm wide) absorption feature centered at ~550 nm. The 550 nm feature, attributed to octahedral Cr3+, is present over a wide range in iron content (Fe# 8–30) and its strength positively correlates with spinel chromium content [ln(reflectancemin) = −0.0295 Cr# – 0.3708]. Our results provide laboratory characterization for the V-NIR and mid-infrared (mid-IR) spectral properties of spinel synthesized at lunar-like f O2. The experimentally determined calibration constrains the Cr# of spinels in the lunar pink spinel anorthosites to low values, potentially Cr# < 1. Furthermore, the results suggest the absence of a 550 nm feature in remote spectra of the Dark Mantle Deposits at Sinus Aestuum precludes the presence of a significant chromite component. Combined, the observation of low chromium spinels across the lunar surface argues for large contributions of anorthositic materials in both plutonic and volcanic rocks on the Moon.

The diffusion kinetics of He and Ne in four amphibole specimens have been experimentally determined using stepwise degassing analysis of samples previously irradiated with energetic protons, and Arrhenius relationships have been fit to these data. The primary finding is that He and Ne diffusivities are systematically lower in amphiboles that have higher concentrations of unoccupied ring sites, suggesting that unoccupied ring sites act as traps for migrating noble gases. Ring site influence of noble gas diffusivity in amphiboles has substantial implications for 40Ar/39Ar thermochronology applied to these phases and the efficiency of noble gas recycling in subduction zones. These findings are consistent with the correlation between noble gas solubility and the concentration of unoccupied ring sites in amphibole (Jackson et al., 2013a, 2015) but are inconsistent with the ionic porosity model for noble gas diffusion (Fortier and Giletti, 1989; Dahl, 1996). Rather, these findings suggest that the topology of ionic porosity and absolute volume of ionic porosity compete in determining the rate at which noble gases diffuse.

Light noble gas (He–Ne–Ar) solubility has been experimentally determined in a range of materials with six-member, tetrahedral ring structures: beryl, cordierite, tourmaline, antigorite, muscovite, F-phlogopite, actinolite, and pargasite. Helium solubility in these materials is relatively high, 4 × 10 −10 to 3 × 10 −7 mol g −1 bar −1 , which is ∼100 to 100,000× greater than He solubility in olivine, pyroxene, or spinel. Helium solubility broadly correlates with the topology of ring structures within different minerals. Distinctive He–Ne–Ar solubility patterns are associated with the different ring structure topologies. Combined, these observations suggest ring structures have a strong influence on noble gas solubility in materials and could facilitate the recycling of noble gases, along with other volatiles (i.e., water, chlorine, and fluorine), into the mantle. Measurements of Ne and Ar solubility in antigorite, however, are highly variable and correlated with each other, suggesting multiple factors contribute the solubility of noble gases in serpentine-rich materials.

The origin of Earth's ancient magnetic field is an outstanding problem. It has recently been proposed that exsolution of MgO from the core may provide sufficient energy to drive an early geodynamo. Here we present new experiments on Mg partitioning between iron-rich liquids and silicate/oxide melts. Our results indicate that Mg partitioning depends strongly on the oxygen content in the iron-rich liquid, in contrast to previous findings that it depends only on temperature. Consequently, MgO exsolution during core cooling is drastically reduced and insufficient to drive an early geodynamo alone. Using the new experimental data, our thermal model predicts inner core nucleation at ~850 Ma and a nearly constant paleointensity.

NASA's Moon Mineralogy Mapper (M 3 ) has identified and characterized a new lunar rock type termed pink spinel anorthosite (PSA) ( Pieters et al., 2011 ). Dominated by anorthitic feldspar and rich in MgAl 2 O 4 spinel, PSA appears to have an unusually low modal abundance of mafic silicates, distinguishing it from known lunar spinel-bearing samples. The interaction between basaltic melts and the lunar crust and/or assimilation of anorthitic plagioclase have been proposed as a possible mechanism for PSA formation ( Gross and Treiman, 2011; Prissel et al., 2012 ). To test these hypotheses, we have performed laboratory experiments exploring magma–wallrock interactions within the lunar crust. Lunar basaltic melts were reacted with anorthite at 1400 °C and pressures between 0.05–1.05 GPa. Results indicate that PSA spinel compositions are best explained via the interaction between Mg-suite parental melts and anorthositic crust. Mare basalts and picritic lunar glasses produce spinels too rich in Fe and Cr to be consistent with the M 3 observations. The experiments suggest that PSA represents a new member of the plutonic Mg-suite. If true, PSA can be used as a proxy for spectrally identifying areas of Mg-suite magmatism on the Moon. Moreover, the presence of PSA on both the lunar nearside and farside ( Pieters et al., in press ) indicates Mg-suite magmatism may have occurred on a global scale. In turn, this implies that KREEP is not required for Mg-suite petrogenesis (as KREEP is constrained to the nearside of the Moon) and is only necessary to explain the chemical make-up of nearside Mg-suite samples.

Remote sensing observations have identified aluminate spinel, in the absence of measureable olivine and pyroxene, as a globally distributed component of the lunar crust. Earlier remote sensing observations and returned samples did not indicate the presence of this component, leaving its geologic significance unclear. Here, we report visible to mid-infrared (V-IR) reflectance (300–25 000 nm) and Mossbauer spectra of aluminate spinels, synthesized at lunar-like oxygen fugacity (ƒO2), that vary systematically in Fe abundance. Reflectance spectra of particulate ( 6 Fe#. Although the 2000 and 2800 nm bands are assigned to Fe 2+ IV electronic transitions, spectra of aluminate spinels with excess Al2O3 demonstrate that the strengths of the 1000 nm bands are related to the abundance of Fe 2+ VI. The abundance of Fe 2+ VI depends on bulk Fe content as well as factors that control the degree of structural order-disorder, such as cooling rate. Consequently the strength of the 1000 nm bands are useful for constraining the Fe content and cooling rate of remotely sensed spinel. Controlling for cooling rate, particle size, and ƒO2, we conclude that spinels with >12 Fe# (

Article history: Magnesium perovskite (MgPv) is likely the first phase to crystallize from a deep magma ocean. Consequently, MgPv crystallization has a strong control on the dynamics and chemical evolution associated with the earliest stages of silicate Earth differentiation. In order to better understand the chemical evolution associated with MgPv crystallization during a magma ocean, a parameterized model for major and trace element partitioning by MgPv has been developed. The parameterization is based on a compilation of published experimental data and is applied to batch and near-fractional crystallization scenarios of ultramafic liquids, allowing for a more complete analysis of the geochemical implications for magma ocean crystallization. The chemical signatures associated with modeled MgPv fractionation are evaluated in the context of possible dynamical outcomes to a magma ocean (e.g. basal magma ocean (BMO) or crystal settling). It is shown that fractionating MgPv from ultramafic liquids imparts diagnostic signatures (e.g. Ca/Al, HFSE anomalies, e 176 Hf-e 143 Nd) in both the liquid and solid phases. These signatures are not currently observed in the accessible Earth, suggesting that either early-fractionating MgPv was subsequently homogenized or crystal suspension was dominant during the earliest stages of magma ocean crystallization. A BMO that fractionates CaPv and MgPv is also considered and shown to mute many of unobserved geochemical effects associated with a MgPv-only fractionation, offering an alternative possibility for the evolution of a BMO depleted in heat producing elements.

Helium partitioning between olivine, orthopyroxene, clinopyroxene, and spinel and basaltic melt has been experimentally determined under upper mantle melting conditions (up to 20 kbar and 1450 °C). Under the conditions explored, helium partition coefficients are similar in all minerals investigated ( K d He ∼ 10 − 4 ), suggesting He is evenly distributed between the minerals of spinel peridotite. This is in contrast to most incompatible elements, which are concentrated in clinopyroxene in spinel peridotite. The studied minerals have different concentrations of point defects, but similar He solubility, providing no evidence for He partitioning onto specific defects sites (e.g. cation vacancies). Upper limits on the partition coefficients for Ne and Ar have also been determined, constraining these elements to be moderately to highly incompatible in olivine at the conditions of spinel peridotite melting ( 10 − 2 and 10 − 3 , respectively). Helium partitioning in peridotite minerals varies little within the range of temperatures, pressures, and mineral compositions explored in this study. Reported partition coefficients, in combination with previous work, suggest that moderate to high degree mantle melting is not an efficient mechanism for increasing (U+Th)/He, (U+Th)/Ne, or K/Ar of the depleted mantle (DMM) through time, and consequently, supports the argument that recycling of oceanic crust is largely responsible for the relatively strong radiogenic noble gas signatures in the depleted mantle. Mantle residues with lowered (U+Th)/He, (U+Th)/Ne, and K/Ar may be produced through large extents of melting, but concentrations of noble gases will be low, unless noble gas solubility in solids deviate from Henryʼs Law at high fugacity.

How noble gases are recycled from the atmosphere back into the mantle has been unclear. High-pressure experiments demonstrate that noble gases are highly soluble in an important hydrous mineral in altered oceanic crust, suggesting that subduction of this type of crust may be a significant pathway for noble gas flux back into the mantle.

Trace element mineral-magma partitioning models are important in understanding processes by which basaltic magmas are generated. Partitioning models for nickel have been extrapolated from their original applicability for the Earth’s mantle to compositions appropriate for other planets, notably the Moon and Mars. Before partitioning models can be extrapolated to explain nickel concentrations in planetary rocks, these models need to be verified thermodynamically and experimentally using planetary basaltic compositions. Experiments conducted in this study on the Martian Gusev Adirondack-class basalt, Humphrey, with 1 wt% nickel in the magma have shown that Ni affects its liquidus phase relations. By stabilizing olivine to higher temperatures, Ni increases the liquidus temperature. These experiments have shown that the Hart and Davis (1978) model based on iron-free systems cannot be extrapolated to planetary, iron-rich, basaltic systems. This work verifies the independence of the Jones (1984, 1995) and Beattie et al. (1991) models from temperature and pressure effects and suggests extrapolation to planetary compositions is justified but needs further verification. Furthermore, these experiments support the Longhi and Walker (2006) hypothesis that at high temperature nickel may be incompatible.